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At least 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Computational Modeling of the Nature and Role of Ga Species for Light Alkane Dehydrogenation Catalyzed by Ga/H-MFI

Ga-exchanged H-MFI zeolites are highly active for the dehydrogenation of light alkanes; however, both the nature of the active gallium species and the associated dehydrogenation mechanism have been difficult to establish. In this study, we examine the activity of Ga species in Ga/H-MFI by calculating the free energy landscapes on which all reactions occur. To this end, we use a hybrid quantum mechanics/molecular mechanics model for all electronic structure calculations. Quantum chemical calculations were carried out with a range-corrected functional and a good representation of dispersive interactions. The molecular mechanics part of our approach captures the long-range effects of Coulombic and dispersive interactions due to atoms in the extended framework. The rate-determining TS (RDTS) is identified by analysis of the free energy landscape for each mechanism, using the energetic span model. Our analysis reveals that, for reduced Ga/H-MFI, univalent and divalent gallium hydrides, [GaH 2 ] + and [GaH] 2+ , respectively, are more active for ethane dehydrogenation in comparison to H + sites and Ga + sites. [GaH] 2+ sites consistently emerge as the most active sites for light alkane dehydrogenation, providing significant enthalpic stabilization to C-H cleavage TSs via alkyl and carbenium dehydrogenation routes. In contrast, carbenium-like C-H cleavage TSs occurring on Brønsted acid sites are enthalpically less favorable due to their limited electronic interactions with framework O atoms and H + sites. Activation enthalpy barriers for dehydrogenation determined using the energetic span analysis are in good agreement with those measured experimentally. Accounting for entropy of activation reveals that constrained TSs become less favorable in free energy with increasing chain length. Here, we also find that an increase in enthalpic favorability of the alkyl mechanism is observed with increasing chain length for the TS responsible for the second C-H cleavage step leading to alkene formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Apparent Activation Energies in Complex Reaction Mechanisms: A Simple Relationship via Degrees of Rate Control

The apparent activation energy of chemical reactions previously played a central role in the field of chemical kinetics and has served as an important tool for analyzing and understanding reaction rates, mechanistic details of complex reaction mechanisms, elementary-step energetics, catalytic activity and reaction selectivity. In this work, we derive a general expression which shows that the apparent activation energy equals a weighted average of the standard-state enthalpies (relative to reactants) of all the species (intermediates, transition states and products) in the reaction mechanism, each weighted by its generalized degree of rate control (DRC). Since the DRC is zero for most of these species, even in very complex mechanisms, the weighted average includes only a few terms. This simplicity provides deep insight into the connection between the reaction energy diagram and the apparent activation energy. We prove both this and the quantitative validity of this equation by analysis of numerous reaction mechanisms. We also show the failures or weaknesses of previous equations for the apparent activation energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Roles of Hydration and Magnetism on the Structure of Ferrihydrite from First Principles

We report density functional theory calculations aimed at predicting thermodynamically stable structures for ferrihydrite across a range of possible compositions determined by the amount of structural water. Based on an assumed formula unit of Fe5O8H + nH2O, we performed ab initio calculations with evolutionary searching to find the lowest enthalpy structures as a function of the water content up to n = 2. This is the most exhaustive search for the ferrihydrite structure conducted so far; more than 5000 unique configurations were generated and evaluated over five states of hydration. Among them, the Michel akdaliate model was generated, along with several energetically comparable new structures at higher states of hydration. However, a direct comparison between calculated and experimental pair distribution function and X-ray diffraction patterns for the 50 lowest energy structures shows that none beyond the Michel model could be associated with ferrihydrite. Nevertheless, this energetically comparable structure set provides a novel basis for analyzing and understanding the effects of hydration and magnetism on the topology of ferrihydrite, from which we conclude that any tetrahedral Fe should be viewed as a metastable structural defect, created either as a result of the rapid kinetics of crystal growth or to accommodate a local magnetic stress between neighboring Fe atoms.

composition, density functional theory, ferrihydri↗
DOE OSTI2023

Dicarbonyl Electrolyte for High-Voltage Lithium Metal Batteries: Importance of the Entropy of Solvation in Bidentate Solvent

An electrolyte system based on dicarbonyl solvents has been proposed and implemented in lithium metal batteries (LMBs). Among several dicarbonyl solvents explored, dimethyl dicarbonate (DMDC) emerged as the most promising electrolyte candidate. Interestingly, despite the structural similarities between DMDC and its monocarbonyl counterpart DMC, the DMDC electrolyte exhibits higher solvent coordination, even at the same lithium-to-carbonyl ratio. Further, this leads to the formation of a more robust solid-electrolyte interphase and enhances the anodic stability of the electrolyte. Notably, in various electrolyte systems, the solvation energy is typically enthalpy-driven. However, the bidentate nature of DMDC introduces a significant role for the entropy of solvation because the Li + -DMDC complexes release fewer free molecules. With the addition of non-solvating co-solvent 1,1,2,2-tetrafluoro-ethyl 2,2,3,3-tetrafluoro-propyl ether (TTE), which reduces the viscosity of the electrolyte, the DMDC-TTE system enables remarkably stable cycling of the lithium anode by manipulating the entropy of solvation. This introduces a new strategy for tailoring functional electrolyte systems.

25 ENERGY STORAGE↗
DOE OSTI2025

Thermodynamics of MgO Atomic Layer Deposition Surface Reactions

The realities of atomic layer deposition (ALD) surface reactions often deviate from the simple ligand exchange frequently used to illustrate the technique. A detailed understanding of these reactions is necessary to develop greater surface synthetic control including chemical selectivity for patterning or to target defects. Here, the thermodynamics of surface reactions relevant to MgO ALD were investigated using pyroelectric calorimetry to measure the time-resolved heat generation. These reactions show exothermic heat generation of 0.12 mJ/cm 2 and 0.15 mJ/cm 2 for alternating Mg(CpEt) 2 and H 2 O reactions, respectively. The total reaction heat closely matches the standard reaction enthalpy for bulk MgO, supplemented with first-principles molecular calculations. First-principles models further reveal that while simple ligand exchange is favorable during surface reactions, the required increase in Mg-coordination number from two in the precursor to six in bulk MgO requires additional coverage-dependent surface reactions, which depend on the availability and stability of proximal surface hydroxyls.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Discrimination of Hexane Isomers by Temperature Swing Adsorption in a Rigid Aluminum Metal–Organic Framework

The efficient separation of alkane isomers with similar physicochemical properties remains a persistent challenge for the petrochemical industry. Adsorptive separation using metal− organic frameworks (MOFs) offers an energy-efficient alternative to conventional distillation. Herein, we report temperature swing discrimination of hexane isomers with different degrees of branching using MIL-120, a rigid aluminum pyromellitate-based MOF. MIL-120 features uniform one-dimensional channels with an aperture of ∼5.5 Å. At 30 °C, it selectively adsorbs linear and monobranched hexanes while excluding the dibranched isomer. Upon heating to 120 °C, both mono- and dibranched isomers are completely excluded, whereas linear hexane remains strongly adsorbed. Breakthrough experiments validate the temperature swing separation performance. Adsorption heat analysis combined with ab initio calculations provides a quantitative measure of distinct differences in adsorption enthalpies, binding energies, and diffusion barriers responsible for the observed separation efficiency, highlighting the potential of this MOF for efficient separation of alkane isomers via temperature swing adsorption.

Adsorption↗
DOE OSTI2022

Hybrid Nanocrystals of Small Molecules and Chemically Disordered Polymers

Organic crystals formed by small molecules can be highly functional but are often brittle or insoluble structures with limited possibilities for use or processing from a liquid phase. A possible solution is the nanoscale integration of polymers into organic crystals without sacrificing long-range order and therefore function. This enables the organic crystals to benefit from the advantageous mechanical and chemical properties of the polymeric component. We report here on a strategy in which small molecules co-crystallize with side chains of chemically disordered polymers to create hybrid nanostructures containing a highly ordered lattice. Synchrotron X-ray scattering, absorption spectroscopy, and coarse-grained molecular dynamics simulations reveal that the polymer backbones form an “exo-crystalline” layer of disordered chains that wrap around the nanostructures becoming a handle for interesting properties. The morphology of this “hybrid bonding polymer” nanostructure is dictated by the competition between the polymers’ entropy and the enthalpy of the lattice allowing for control over the aspect ratio of the nanocrystal by changing the degree of polymer integration. Further, we observed that nanostructures with an exo-crystalline layer of polymer exhibit enhanced fracture strength, self-healing capacity, and dispersion in water, which benefits their use as light-harvesting assemblies in photocatalysis. Guided by computation, future work could also explore these hybrid nanostructures as building blocks for functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Enhancing Room-Temperature Hydrogen Storage Properties in Ti–V–Cr–Nb–Mo/Fe Multielement Alloys via Substitutional Tuning

Building upon previously reported high-entropy alloys (HEA) in the Ti−V−Cr−Nb−Mo/Fe compositional space, this study presents a novel bcc alloy containing 6 at. % of the earthabundant element Fe, exhibiting enhanced hydrogen storage properties at room temperature (25 °C). The optimized bcc Ti 23 V 30 Nb 10 Cr 31 Fe 6 alloy rapidly absorbs hydrogen at room temperature with a maximum gravimetric capacity of 3.4 wt % and an enthalpy of hydride formation of −34 kJ/mol H 2 . This value is among the lowest reported to date for bcc HEAs. The reversible capacity of this alloy remains stable at 2.0 wt % upon 20 absorption/desorption cycles at room temperature, which is among the highest reported values for this material class. Collectively, these advances highlight the potential of Fecontaining multielement alloys as efficient and economical candidates for next-generation hydrogen storage systems.

08 HYDROGEN↗
DOE OSTI2022

Process Model-Based Validation of the Intensification of Biomass Fast Pyrolysis in a Fluidized Bed via Autothermal Operation

A model for the fluidized-bed pyrolysis of biomass is extended to enable the simulation of intensified autothermal operation. In this system, partial oxidation of char and pyrolysate species replaces an external heat source to supply the enthalpy of pyrolysis, greatly increasing the throughput of a given fast pyrolysis reactor. Oxidation reactions are compiled from CRECK and other literature sources and extended to cover the species found in pyrolysis products, including a derivation of the catalytic effect of ash on char combustion from experimental studies at Iowa State University (ISU). Results indicate a roughly 3-fold increase in biomass throughput for a given reactor volume at the pilot scale with minimal loss of valuable products, in agreement with published data from the 3 × 10 -2 m 3 reactor operated by ISU. Additionally, a proposal for a 250 ton/day commercial-scale biomass pyrolysis reactor is analyzed, showing that the same size reactor operated by heating the fluidizing gas externally would have only one-tenth the capacity; if operated by heating the sand externally, the sand would need to circulate at an impractical 0.7 bed volume per minute rate to maintain a 250 ton/day biomass throughput.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Density Functional Theory Study of Spirodienone Stereoisomers in Lignin

The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ~3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a ..beta..-1 bond, has been proposed to be a precursor for acyclic ..beta..-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentally observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C-O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.

09 BIOMASS FUELS↗
DOE OSTI2015

Active Site and Remote Contributions to Catalysis in Methylthioadenosine Nucleosidases

5'-Methylthioadenosine/S-adenosyl-l-homocysteine nucleosidases (MTANs) catalyze the hydrolysis of 5'-methylthioadenosine to adenine and 5-methylthioribose. The amino acid sequences of the MTANs from Vibrio cholerae (VcMTAN) and Escherichia coli (EcMTAN) are 60% identical and 75% similar. Protein structure folds and kinetic properties are similar. However, binding of transition-state analogues is dominated by favorable entropy in VcMTAN and by enthalpy in EcMTAN. Catalytic sites of VcMTAN and EcMTAN in contact with reactants differ by two residues; Ala113 and Val153 in VcMTAN are Pro113 and Ile152, respectively, in EcMTAN. Here, we mutated the VcMTAN catalytic site residues to match those of EcMTAN in anticipation of altering its properties toward EcMTAN. Inhibition of VcMTAN by transition-state analogues required filling both active sites of the homodimer. However, in the Val153Ile mutant or double mutants, transition-state analogue binding at one site caused complete inhibition. Therefore, a single amino acid, Val153, alters the catalytic site cooperativity in VcMTAN. The transition-state analogue affinity and thermodynamics in mutant VcMTAN became even more unlike those of EcMTAN, the opposite of expectations from catalytic site similarity; thus, catalytic site contacts in VcMTAN are unable to recapitulate the properties of EcMTAN. X-ray crystal structures of EcMTAN, VcMTAN, and a multiple-site mutant of VcMTAN most closely resembling EcMTAN in catalytic site contacts show no major protein conformational differences. In conclusion, the overall protein architectures of these closely related proteins are implicated in contributing to the catalytic site differences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

General Method for Determination of the Surface Composition in Bimetallic Nanoparticle Catalysts from the L Edge X-ray Absorption Near-Edge Spectra

Bimetallic PtPd on silica nano-particle catalysts have been synthesized and their average structure determined by Pt L3 and Pd K-edge extended X-ray absorption finestructure (EXAFS) spectroscopy. The bimetallic structure is confirmed from elemental line scans by STEM for the individual 1-2 nm sized particles. A general method is described to determine the surface composition in bimetallic nanoparticles even when both metals adsorb, for example, CO. By measuring the change in the L3 X-ray absorption near-edge structure (XANES) spectra with and without CO in bimetallic particles and comparing these changes to those in monometallic particles of known size the fraction of surface atoms can be determined. The turnover rates (TOR) and neopentane hydrogenolysis and isomerization selectivities based on the surface composition suggest that the catalytic and spectroscopic properties are different from those in monometallic nano-particle catalysts. At the same neo-pentane conversion, the isomerization selectivity is higher for the PtPd catalyst while the TOR is lower than that of both Pt and Pd. As with the catalytic performance, the infrared spectra of adsorbed CO are not a linear combination of the spectra on monometallic catalysts. Density functional theory calculations indicate that the Pt-CO adsorption enthalpy increases while the Pd-CO bond energy decreases. The ability to determine the surface composition allows for a better understanding of the spectroscopic and catalytic properties of bimetallic nanoparticle catalysts.

bimetallic↗
DOE OSTI2013

Tests of Exchange-Correlation Functional Approximations Against Reliable Experimental Data for Average Bond Energies of 3d Transition Metal Compounds

One of the greatest challenges for the theoretical study of transition-metal-containing compounds is the treatment of intrinsically multi-configurational atoms and molecules, which require a multireference (MR) treatment in wave function theory. The accuracy of density functional theory for this kind of system is still being explored. Here, we continue that exploration by presenting the predictions of 42 exchange-correlation (xc) functionals of 11 types [local spin density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta-GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)]. DFT-D is tested both for Grimme’s DFT-D3(BJ) model with Becke-Johnson damping and for ωB97X-D, which has the empirical atom-atom dispersion parametrized by Chai and Head-Gordon. The Hartree-Fock (HF) method has also been included because it can be viewed as a functional with 100% HF exchange and no correlation. These methods are tested against a database including 70 first-transition-row (3d) transition metal-containing molecules (19 single-reference molecules and 51 MR molecules), all of which have estimated experimental uncertainties equal to or less than 2.0 kcal/mol in the heat of formation. We analyze the accuracy in terms of the atomization energy per bond instead of the enthalpy of formation of the molecule because it allows us to test electronic energies without the possibility of cancellation of errors in electronic energies with errors in vibrational energies. All the density functional and HF wave functions have been optimized to a stable solution, in which the spatial symmetry is allowed to be broken to minimize the energy to a stable solution. We find that Ï„-HCTHhyb has the smallest mean unsigned error (MUE) in average bond energy, in particular 2.5 kcal/mol, for the full set of 70 molecules, and it also gives the smallest MUE for MR systems. For single-reference systems, MPW1B95 has the best performance, with an MUE of 1.6 kcal/mol. Among local functionals, which are the least expensive, the best performance (MUE = 3.9 kcal/mol) for the total database is achieved by OreLYP, OLYP, M06-L, and τ-HCTH. It is observed that adding HF exchange does not guarantee better accuracy for GGAs or for the NGA, but inclusion of the kinetic energy densities can benefit the GGAs and NGA calculations. The metal hydrides and metal oxides are demonstrated to be most difficult bond types to predict, and CrO 3 , FeH, CrO, VH and MnS are found to be the most difficult molecules to predict. The middle transition metals (V, Cr, and Mn) lead to larger errors on average than either the early or late transition metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Membrane-Based Osmotic Heat Engine with Organic Solvent for Enhanced Power Generation from Low-Grade Heat

We present a hybrid osmotic heat engine (OHE) system that uses draw solutions with an organic solvent for enhanced thermal separation efficiency. The hybrid OHE system produces sustainable energy by combining pressure-retarded osmosis (PRO) as a power generation stage and membrane distillation (MD) utilizing low-grade heat as a separation stage. While previous OHE systems employed aqueous electrolyte draw solutions, using methanol as a solvent is advantageous because methanol is highly volatile and has a lower heat capacity and enthalpy of vaporization than water. Hence, the thermal separation efficiency of a draw solution with methanol would be higher than that of an aqueous draw solution. In this study, we evaluated the performance of LiCl-methanol as a potential draw solution for a PRO-MD hybrid OHE system. The membrane transport properties as well as performance with LiCl methanol draw solution were evaluated using thin-film composite (TFC) PRO membranes and compared to the results obtained with a LiCl water draw solution. Experimental PRO methanol flux and maximum projected power density of 47.1 L m(-2) h(-1) and 72.1 W m(-2), respectively, were achieved with a 3 M LiCl-methanol draw solution. The overall efficiency of the hybrid OHE system was modeled by coupling the mass and energy flows between the thermal separation (MD) and power generation (PRO) stages under conditions with and without heat recovery. The modeling results demonstrate higher ORE energy efficiency with the LiCl methanol draw solution compared to that with the LiCl water draw solution under practical operating conditions (i.e., heat recovery <90%). We discuss the implications of the results for converting low-grade heat to power.

Shaulsky, E↗
DOE OSTI2010

Thermochemistry of Lewis Adducts of BH 3 and Nucleophilic Substitution of Triethylamine on NH 3 BH 3 in Tetrahydrofuran

The thermochemistry of the formation of Lewis base adducts of BH 3 in tetrahydrofuran (THF) solution and the gas phase and the kinetics of substitution on ammonia borane by triethylamine are reported. The dative bond energy of Lewis adducts were predicted using density functional theory at the B3LYP/DZVP2 and B3LYP/6-311+G** levels and correlated ab initio molecular orbital theories, including MP2, G3(MP2), and G3(MP2)B3LYP, and compared with available experimental data and accurate CCSD(T)/CBS theory results. The analysis showed that the G3 methods using either the MP2 or the B3LYP geometries reproduce the benchmark results usually to within ~1 kcal/mol. Energies calculated at the MP2/aug-cc-pVTZ level for geometries optimized at the B3LYP/DZVP2 or B3LYP/6-311+G** levels give dative bond energies 2-4 kcal/mol larger than benchmark values. The enthalpies for forming adducts in THF were determined by calorimetry and compared with the calculated energies for the gas phase reaction: THFBH 3 + L → LBH 3 + THF. The formation of NH 3 BH 3 in THF was observed to yield significantly more heat than gas phase dative bond energies predict, consistent with strong solvation of NH 3 BH 3 . Substitution of NEt 3 on NH 3 BH 3 is an equilibrium process in THF solution (K ≈ 0.2 at 25 °C). The reaction obeys a reversible bimolecular kinetic rate law with the Arrhenius parameters: log A = 14.7 ± 1.1 and E a = 28.1 ± 1.5 kcal/mol. Finally, simulation of the mechanism using the SM8 continuum solvation model shows the reaction most likely proceeds primarily by a classical S N 2 mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Complexation of Lactate with Nd(III) and Eu(III) at Variable Temperatures: Studies by Potentiometry, Microcalorimetry, Optical Absorption and Luminescence Spectroscopy

Complexation of neodymium(III) and europium(III) with lactate was studied at variable temperatures by potentiometry, absorption spectrophotometry, luminescence spectroscopy and microcalorimetry. Stability constants of three successive lactate complexes (ML{sup 2+}, ML{sup 2+} and ML{sub 3}(aq), where M stands for Nd and Eu, and L stands for lactate) at 10, 25, 40, 55 and 70 C were determined. The enthalpies of complexation at 25 C were determined by microcalorimetry. Thermodynamic data show that the complexation of trivalent lanthanides (Nd{sup 3+} and Eu{sup 3+}) with lactate is exothermic, and the complexation becomes weaker at higher temperatures. Results from optical absorption and luminescence spectroscopy suggest that the complexes are inner-sphere chelate complexes in which the protonated {alpha}-hydroxyl group of lactate participates in the complexation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗